JPH02103057A - Liquid developing agent for electrostatic photography - Google Patents

Abstract

PURPOSE:To obtain a liquid developing agent for electrostatic photography which can be dispersed stably by polymerizing a specified monomer in a soln. CONSTITUTION:A liquid developing agent for electrostatic photography having high dispersion stability of dispersed resin particles is obtd. by constituting the dispersed resin of a polymer obtd. by polymerizing at least one kind of monofunctional monomers (A) contained in a soln. with at least one kind of monomers (B) having at least two basic joint groups expressed by the formula II and/or polar groups in a soln. in the presence of a resin for improving stability of dispersibility which is prepd. by bonding a copolymerizable double bond with the monomer (A) at only one terminal of a principal chain of a polymer having at least one recurrent unit expressed by the formula I. In the formula I, X is -COO-, -OCO-, etc.; R1 is a 6-32C aliphatic group; each a<1> and a<2> is an H atom, halogen atom, cyano group. In the formula II, V is -O-, -COO-, -OCO-, etc.; Q is an H atom, halogen atom, etc.; each X1 and X2 is -O-, -S-, -CO-, -CO2-, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a liquid developer for electrostatic photography comprising at least a resin dispersed in a carrier liquid having an electrical resistance of 10'Ωcm or more and a dielectric constant of 3.5 or less. In particular, it relates to a liquid developer with excellent redistribution properties, storage stability, stability, image reproducibility, and fixing properties.

(Prior art) General liquid developers for electrophotography are made by combining organic or inorganic pigments or dyes such as carbon black, nigrosine, and fucrocyanine blue with natural or synthetic resins such as alkyd resins, acrylic resins, rosins, and synthetic rubbers. It is dispersed in a liquid with high insulating properties and low dielectric constant, such as aliphatic hydrocarbons, and a polarity control agent such as metal soap, lecithin, linseed oil, higher fatty acids, or a polymer containing vinyl pyrrolidone is added. be.

In such developers, the resin is dispersed as insoluble Latinx particles with a diameter of several nanometers to several hundred nanometers, but in conventional liquid developers, the resin is incompatible with the soluble dispersion stabilizing resin and polarity control agent. Since the bonding with the soluble Latinx particles was insufficient, the soluble molecule IT stabilizing resin and the polarity control agent were likely to diffuse into the solution. Therefore, after long-term storage or repeated use, the volume dispersion stabilizing resin may be detached from the insoluble latex particles, causing the particles to settle, aggregate, or accumulate, or become polarized or unclear. Ta.

In addition, since the particles that have aggregated and accumulated are difficult to redisperse, the particles remain attached to various parts of the developing machine, leading to problems with the developing machine such as staining of the image area and clogging of the liquid feed pump.

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble latex particles has been devised and disclosed in US Pat. No. 3,990,980 and the like. However, although the dispersion stability of these liquid developers against natural sedimentation of particles has improved to some extent, it is still not sufficient, and when used in an actual developing device, the toner that adheres to various parts of the device forms a film. This has the drawback that it is difficult to redisperse, and furthermore, it causes equipment failure, lη deviation of copied images, etc., and is insufficient for practical redistribution+lk stability. In the method for producing resin particles described above, in order to produce monodisperse particles with a narrow particle size distribution, the dispersion stabilizer used,
There are significant restrictions on the combination of insolubilizing monomers, and the result is generally particles with a wide particle size distribution containing a large amount of coarse particles, or polydisperse particles with two or more average particle sizes. In addition, it is difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 1 μm or more or 0.5 μm or more are difficult to obtain.
Very fine particles of 1 μm or less were formed. Furthermore, there are problems in that the dispersion stabilizer used must be manufactured through a complicated and time-consuming manufacturing process.

Furthermore, in order to improve the above-mentioned drawbacks, insoluble dispersed resin particles of a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety or a monomer containing two or more kinds of scratching components are used. A method of improving the dispersibility, redispersibility, and storage stability of particles by doing so is disclosed in JP-A-60-179751 and JP-A-62-151868. In addition, insoluble dispersed resin particles of a copolymer of a monomer that becomes insolubilized in the presence of a polymer using a difunctional monomer or a polymer using a polymer reaction and a monomer containing a long-chain alkyl moiety. A method for improving the dispersity, redispersibility, and storage stability of particles by
It is disclosed in No. 6366567 and the like.

(Problem to be Solved by the Invention) On the other hand, in recent years, a method of printing 5,000 or more sheets using a master plate for off-cent stamps using an electrophotographic method has been attempted, and improvements in the master plate in particular have been made. It has become possible to print more than 10,000 sheets in plate size. Further, the operating time of electrophotographic engraving systems has been shortened, and improvements have been made to speed up the development and fixing process.

JP-A-60-179751 and JP-A No. 62-15186
8, No. 62-166362, and No. 63-66567, the dispersion resin particles produced according to the means disclosed in No. 8, No. 62-166362, and No. 63-66567 have problems in terms of particle dispersibility, redispersibility, and fixation when the development speed increases. In cases where the time is shortened or in the case of a master plate of large size (for example, A-3 size or larger), the performance is still not necessarily satisfactory in terms of rigidity resistance.

The present invention solves the problems of conventional liquid developers as described above.

It is an object of the present invention to provide a liquid developer that can speed up the development and fixation process and has excellent stability, redispersibility, and fixation properties even in an electrophotolithography system using a large-size master plate. It is to provide.

Another object of the present invention is to provide a liquid developer that enables the production of offset printing original plates having 41-ray printing ink sensitivity and printing durability by electrophotography.

Another object of the present invention is to provide a liquid developer suitable for various electrostatic photographs and various transfer applications in addition to the above-mentioned applications.

Still another object of the present invention is to provide a liquid developer which can be used in any system where a liquid developer can be used, such as inkjet recording, cathode ray tube recording, and recording of various change processes such as pressure changes or electrostatic changes. It is to provide.

(Means for Solving the Problems) An object of the present invention is to provide an electrostatic photographic liquid developer comprising at least a resin dispersed in a nonaqueous solvent having an electrical resistance of 10 qΩcm or more and a dielectric constant of 3.5 or less. The dispersed resin particles contain a polymerizable dihydrogen copolymerizable with the monofunctional monomer (A) only at one end of the main chain of the polymer having at least one repeating unit represented by the following general formula (I). In the presence of a dispersion stabilizing resin comprising a polymeric bonding group, a monofunctional monomer (A) which is soluble in the nonaqueous solvent but becomes insolubilized by polymerization, and a monomer of the following general formula (II
) Copolymer resin particles obtained by polymerizing a solution containing at least one monomer (B) containing at least two or more polar groups and/or polar linking groups. This was achieved by an electrostatographic liquid developer characterized by the following.

General formula (I) %Formula% In general formula (I), X is -COO-8-OCO-1-CI
1.0CO-1CIl□COO-1-〇-1 or -3O
□ Represents -.

R1 represents an aliphatic group having 6 to 32 carbon atoms.

a+ and a2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-R'' or a hydrocarbon group having 1 to 8 carbon atoms. -COO-R"(R" represents a hydrocarbon group having 1 to 22 carbon atoms).

General formula (It) ul and U2 may be the same or different, and in formula (II), ■ is -0COO-1-OCO-1 C1120CO-2-SO□-, -CONII-1 -S
Bonding group in O□N11-, -CON: Represents the same content as +U'x1)T+Urx City=RO.) Q is a hydrogen atom or a halogen atom, -011, -CN
, Nl+□, -COOII, -3o311 or -1'O, 11□ represents a hydrocarbon group having 1 to 18 carbon atoms.

× and ×2 may be the same or different from each other, respectively -0-1 to S--CO-1-CO2--0CO-, -5
ol or -NIICONI+- (mouth l+ 11
t, 01, mouth, and Q indicate the same contents as Q above).

(X, , x4 may be the same or different from each other and have the same contents as x1 and x2 above, and U is an optionally substituted carbon number of 1). ~ 18 hydrocarbon group, and '' indicates the same content as Q above]
Represents a hydrocarbon group having 1 to 18 carbon atoms.

bl and b2 may be the same or different, and each represents a hydrogen atom, a hydrocarbon group, -Coo-L, or -coo-L via a hydrocarbon (L is a hydrogen atom or an optionally substituted hydrocarbon group). ).

m, n and p may be the same or different and each represents an integer from 0 to 4.

Hereinafter, the liquid developer of the present invention will be explained in detail.

The carrier liquid having an electrical resistance of 10''Ωcm or more and a dielectric constant of 3.5 or less used in the present invention is preferably a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon; Halogen substitutes can be used, such as octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, Hensen, toluene, xylene, mesotylene, Isopar 1 Exopar G, Isopar H, Isopar L (isopar 1
Exxon's product name), Shellzol 70, Shellzol 71 (Shellzol; Shell Oil Company's product name),
Amsco OMS, Amsco 460tQ agent (Amsco; trade name of Subirisotsu Co., Ltd.), etc. are used alone or in combination.

Non-aqueous dispersed resin particles (hereinafter sometimes referred to as Latinx particles), which are the most important component in the present invention, have only one end of the polymer main chain in a non-aqueous solvent.
In the presence of a dispersion stabilizing resin formed by bonding a polymerizable double bond group that can be copolymerized with the monofunctional monomer (A), the monofunctional monomer (A) and the intermediate polymer (B) are combined. It is produced by polymerization and granulation by copolymerizing and granulating.

Here, as the non-aqueous solvent, basically any solvent can be used as long as it is miscible with the carrier liquid of the electrostatic photographic liquid developer.

That is, the solvent used in producing the dispersed resin particles may be any solvent as long as it is miscible with the carrier liquid, and preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. and halogen-substituted products thereof. For example, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, Isopar E, Isopar G, Isopar H, Isopar 1 Schierzolf 0. Sielzur 71. Amsco OMS, Amsco 460? 87t'
1 etc. are used alone or in combination.

Solvents that can be used in combination with these organic solvents include alcohols (e.g., methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.), Carboxylic acid esters (e.g. methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (For example, methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methylchloroform, etc.).

It is preferable that the non-aqueous solvent used in the mixture be removed by heating or distillation under reduced pressure after polymerization and granulation, but even if it is brought into the liquid developer as a latex particle dispersion, it will not affect the liquid in the developer. There is no problem as long as the resistance satisfies the condition of 1O'Ωcm or more.

Usually, it is preferable to use the same solvent as the carrier liquid at the stage of producing the resin dispersion, and as mentioned above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons,
Examples include halogenated hydrocarbons.

This book is used to make a stable resin dispersion of a solvent-insoluble copolymer produced by copolymerizing a monofunctional monomer (A) and a monomer (B) in a non-aqueous solvent. The dispersion stabilizing resin of the invention contains only a small number of repeating units represented by the formula (I) (including one type only at one end of the polymer main chain, which is copolymerizable with the monofunctional monomer (A)). It is a polymer formed by bonding polymerizable double bond groups.

-II In the repeating unit represented by formula (I), aliphatic groups and hydrocarbon groups may be substituted.

In general formula (I), X is preferably -COO-1O
CO--ClhOCO-1-CIl, C00- or -0
-, more preferably -000-1-C11□C
Represents OO- or -〇-.

R1 preferably represents an optionally alkyl group, alkenyl group or aralkyl group having 8 to 22 carbon atoms. Examples of the IAW include halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), -0-R'
-Coo-R'' -0CO-113 (R' represents an alkyl group having 6 to 22 carbon atoms, such as hexyl group,
Octyl group, decyl group, dodecyl group, hexadecyl group,
Examples include substituents such as octadecyl group, etc.). More preferably, R1 represents an alkyl group or an alkenyl group having 8 to 22 carbon atoms, such as an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a docosanyl group, an octenyl group, Decenyl group, dodecenyl group, tetradecenyl group,
Examples include octadecenyl group.

als C2 may be the same or different, preferably a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyan group, a carbon number of 1 to
3 alkyl group, -Coo-R" or Cl1fCOO
-R"(R" preferably represents an aliphatic group having 1 to 22 carbon atoms). More preferably, al, C2 are
May be the same or different, hydrogen atom, carbon number 1~
3 alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), -COO-R" or CIl□C00-R"
(R" more preferably represents an alkyl group or an alkenyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group,
Examples include decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, etc.
These alkyl groups and alkenyl groups may have the same substituents as those represented by R1 above.

The polymerizable double bond group bonded to one end of the polymer main chain is a group copolymerizable with the monofunctional monomer (A), specifically, ICl1□=CI+-0-CCl1 □=Cl-Cl+□-〇-〇C11,0 ciIz=c-o-c-1 CIl□・Cl1-3O.

I C1+□=(j+-C-2CI,=CI+-0CH2I
ICIl-5 C112=CI+-1 CIl□, CI(-CI+□, etc.) can be mentioned.

These polymerizable double bond groups have a chemical structure in which they are directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group.

Linking groups include carbon-carbon bonds (-double bonds or double bonds), carbon-heteroatom bonds (heteroatoms include:
For example, it is composed of any combination of atomic groups such as oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, and heteroatom-heteroatom bonds. For example, (-C)-(R'
, R5 is a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an ano group, a hydroxyl group, an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.) R7 is a hydrogen atom, R represented by general formula (I)
Examples include a single linking group selected from atomic groups such as (representing a hydrocarbon group having the same meaning as 2) or a linking group composed of any combination thereof.

The polymer component of the dispersion stabilizing resin of the present invention is represented by -i formula (I)
A homopolymer component or a copolymer component selected from the repeating units represented by formula (I) or a monomer corresponding to the repeating unit represented by general formula (I) is polymerized with other monomers that can be polymerized. It is composed of a copolymer component obtained by Other monomers that can be used as copolymer components together with the polymer component of general formula (I) include, for example, compounds represented by the following general formula (I).

General formula (III) ld2 0- -3- -C-, -N--COO--5ow
In general formula (II), T is -COO-1-OCO-1-C
11,0CO-1. Here, R9 represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 1 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2- cyanony 1
-ru group, 2-hydroxyethyl group, hensyl group, chlorohensyl group, methylhensyl group, methoxybenzyl group,
Phenethyl group, 3-phenylpropyl group, dimethylhensyl group, fluorohensyl group, 2-methoxyethyl group, 3
-methoxypropyl group, etc.).

R8 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 22-dichloroethyl L
2.2.2-1-IJ Fluoroethyl Maki, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2.3-dihydroxyethyl group, 2-hydroxy-3-chloro propyl group,
2-anoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, NN-dimethylaminoethyl group, N,N-diethylaminoethyl group, trimethoxysilylpropyl group, 3-bromopropyl group,
4-hydroxybutyl group, 2-furfurylethyl group, 2
-thienylethyl group, 2-pyridylethyl group, 2-morpholinoethyl method, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-hostethyl group, 3-sulfopropyl group, 4- Sulfobutyl group, 2-carboxyamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxyamidoethyl group,
cyclopentyl group, chlorochlorohexyl group, dichlorohexyl group, etc.).

d+ and R2 may be the same or different, and each represents the same content as al or R2 in the general formula (I).

Specific monomers represented by general formula (III) include:
For example, vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, acetic acid, monochloroacetic acid, trifluoropropionic acid, etc.), acrylic acid, meccrylic acid, crotonic acid, itaconic acid, C1-4 optionally substituted alkyl esters or amides of unsaturated carboxylic acids such as maleic acid (alkyl groups such as methyl, ethyl, propyl,
Butyl group, 2-chloroethyl group, 2-bromoethyl group,
2-fluoroethyl group, trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methquinethyl group, 2-methanesulfonylethyl group, 2-henzenesulfonylethyl group, 2-( N,
N-dimethylamino)ethyl group, 2-(N,N-diethylamino)ethyl group, 2-carboxyethyl group, 2
-Phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl convex, 4-sulfobutyl group, 3-chlorofurohyl group, 2-hydroxy-3-chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2- thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.), styrene derivatives (e.g., styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene,
Furomostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N,N-dimethylaminomethylstyrene, vinylhenzenecarpoxyamide, vinylbenzenesulfonic acid, etc.), acrylic acid , unsaturated carboxylic acids such as methacrylic acid, crotonic acid, maleic acid, itaconic acid or cyclic anhydrides of maleic acid and itaconic acid, acrylonitrile, meccrylonitrile,
Heterocyclic compounds containing polymerizable double bond groups (specifically,
For example, "Polymer Data Handbook - Basic Edition -" published by the Society of Polymer Science, 2175-184, Baifukan (published in 1986)
(eg, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.).

Two or more types of monomers represented by general formula (ill) may be used in combination.

The repeating unit represented by the above general formula (I) accounts for 30% by weight or more in the dispersion stabilizing resin polymer used in the present invention.
100% by weight is suitable, preferably 50% by weight to 1
00ffl amount%.

The dispersion stabilizing resin of the present invention, which has a polymerizable double bond group bonded only to one end of the polymer main chain, has various double bonds at the end of a living polymer obtained by conventionally known anionic or cationic polymerization. Reacting with a reagent containing a group or adding a specific reactive group (e.g. -011, -COOI+, ~
SO, H, -Nl+□, -311, etc.) is reacted with a reagent, and then a polymerizable double bond group is introduced by a polymer reaction (ionic polymerization method), or the above-mentioned into the molecule After radical polymerization using a polymerization initiator and/or chain transfer agent containing a specific reactive group, a specific reactive group bonded only to one end of the polymerizable main chain is used. It can be easily produced by a synthetic method such as a method in which a polymerizable double bond group is introduced by conducting a polymer reaction.

Specifically, P, Dreyfuss & R,P,
QuirkEncycle, l'olym, Sci,
Eng,, 7.551 (I987), Yoshiki Nakajo,
Tatsuya Yamashita, [Somene 4 and Yakuhin J, 30.232 (I9
85), Akira Ueda, Susumu Nagai, “Science and Industry”, Tei 57
(I986), P. P. Rempp &amp;
E, Franta, eight advancesin
Polymer 5science+ 58+ 1 (I
984), Hiroshi Ito - “Polymer Processing J, 35.262
(I98G), ν, Percec+Applied
Polymer 5science, 285, 9
7 (I984) and the literature cited therein.

The weight average molecular weight of the dispersion stabilizing resin used in the present invention is lX
Preferably 10' to 5X10', more preferably 2X1
0' to 2X10'.

Specific examples of the dispersion stabilizing resin used in the present invention are shown below, but the present invention is not limited thereto.

C1l.

IL (I i': 1L (I C1+.

CI+3 CI+ H3 CI+.

(+-7) (+-8) C11゜ C.I.

C, 11゜C00I+ (I) The monomers used in producing the non-aqueous dispersion resin include a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insoluble upon polymerization. , at least two polar groups and/or polar linking groups represented by the general formula (II)
The monomer (B) can be divided into monomers (B) which contain at least two monomers and copolymerize with the lift form (A).

The monomer (A) in the present invention may be any monofunctional monomer that is soluble in a nonaqueous solvent but becomes insolubilized by polymerization. Specifically, for example, the general formula (I
Examples include monomers represented by V).

General formula (IV) II Cll=C Tl-1?10 In general formula (IV), Tl is -COO-1-OCO-1-
cuzoc.

represents. Here 1711 is a hydrogen atom or carbon number 1
~18 optionally substituted aliphatic groups (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, Chlorobenzyl group, methylbenzyl group, methoxyhensyl group, phenethyl group,
3-phenylpropyl group, dimethylbenzyl group, fluorohensyl group, 2-methoxyethyl group, 3-methoxypropyl group, etc.).

R16 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group,
Butyl group, 2-chloroethyl group, 2゜2-dichloroethyl group, 2,2.2-trifluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2.3-dihydroxyethyl group, 2-hydroxy-3-chloropropyl group,
2-cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methquinethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, NN-dimethylaminoethyl group, N,N-diethylaminoethyl group, Methoxysilylpropyl group, 3-bromopropyl group,
4-hydroxybutyl group, 2-furfurylethyl group, 2
-thienylethyl group, 2=pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group , 2-carboxyamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxyamidoethyl group'
, cyclopentyl group, chlorochlorohexyl group, dichlorohexyl group, etc.).

el and e2 may be the same or different, and each represents the same content as al or a2 in the general formula (I).

Specific monofunctional monomers (A) include, for example, vinyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.) or allyl esters, optionally substituted alkyl esters or amides having 1 to 4 carbon atoms of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid (as an alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, 2
-ri tetraloethyl group, 2-bromoethyl group, 2-fluoroethyl group, trifluoroethyl group, 2hydroxyethyl group,
2-cyanethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-(N,N-dimethylamine)ethyl group, 2-(N, N-diethylamino)ethyl group, 2-carboxyethyl group, 2-phosphoethyl group, 4
-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroquine-3-chloropropyl group, 2-furfurylethyl group, 2-
pyridinylethyl group, 2-thienylethyl group, trimethquinsilylpropyl group, 2-carboxyamidoethyl group, etc.), styrene derivatives (e.g. styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene) , vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, NN-dimethylaminomethylstyrene, vinylhenzenecarboxamide, vinylbenzenesulfonic acid, etc.), acrylic acid, methacrylic acid, Unsaturated carboxylic acids such as crotonic acid, maleic acid, and itaconic acid, or cyclic anhydrides of maleic acid and itaconic acid, acrylonitrile, methacrylonitrile, and heterocyclic compounds containing a polymerizable double bond group (specifically, for example, , "Polymer Data Handbook - Basic Edition - J," edited by the Society of Polymer Science and Technology, p. 175~
184, Baifukan (published in 1986), such as N-vinylpyridine, N-vinylthiazole, N-
Vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxaprine, vinylthiazole,
N-vinylmorpholine, etc.).

Two or more monofunctional monomers (A) may be used in combination.

Next, the monomer (B) represented by the general formula (■) used in the present invention will be further explained.

In the general formula ((I), preferably, ■ is -0-1匈COO--0CO--CIl□0CO-1-CONII
- or -CON [W is preferably an optionally substituted alkyl group having a total of 1 to 16 carbon atoms, an optionally substituted alkenyl group having a total of 2 to 16 carbon atoms, an optionally substituted alkenyl group having a total of 5 to 18 carbon atoms Alicyclic group or bonding group in general formula (II): +U+
L+-+-'bXz→T-(indicates the same content as l).

Q is preferably a hydrogen atom or a halogen atom (e.g. chloro atom, bromo atom, etc.), -011, -CN, C
It represents an aliphatic group having a total of 1 to 16 carbon atoms (the aliphatic group is, for example, an alkyl group, an alkenyl group, or an aralkyl group) which may be substituted with 0OH.

X and X2 may be the same or different, preferably 10-1-S--CO-1-coo--oc.

- indicates the contents).

U and U2 may be the same or different from each other, preferably a substituted or optional hydrocarbon group having 1 to 12 carbon atoms (the hydrocarbon group includes an alkylene group, an alkenylene group, an arylene group). or cycloalkylene group).

However, χ3 and ×4 may be the same or different.
2, U4 preferably represents an optionally substituted alkylene group, alkenylene group, or arylene group having 1 to 12 carbon atoms, and Q6 has the same contents as Q above.

bl and b2 may be the same or different, preferably a hydrogen atom, a methyl group, -COO-L or C1
hCOO-L (L is preferably a hydrogen atom, carbon number 1
~1B represents an alkyl group, alkenyl group, aralkyl group or cycloalkyl group).

Furthermore, m, n and p may each be the same or different,
Preferably, it represents a number of 0.1.2.3.

More preferably, in formula (n), ■ is composed of 8 or more. Here, hydrogen atom, methyl group, C00-L or -CIl may be the same or different.
□C00-L (L is more preferably a carbon number of 1 to 12
represents an alkyl group).

Furthermore, regarding Ul and U2, specific examples include alkyl group, halogen atom, etc.), →CH= CH)-
1 and p have the same meanings as the above symbols).

Further, in the bonding group in general formula (n): V +1Il-X++r+Uz-Xz→, Q,
■ to Q (i.e. V, u, , xl, U2, X2 and Q
) has a total number of atoms of +0l-xl
-h+-U2-x2→,[1] A connecting main chain composed of W is also included in the connecting main chain. Furthermore, Ul,
U2 connects -C11- to main chain Xs +lla Xa'h-
In the case of the hydrocarbon group interposed in the bond of 'Ib, 1X3,04-x4 catty-〇 is also the number of atoms in the 6-connected main chain included in the above-mentioned connected main chain. For example, ■ is COO- or -C
When representing ON)l-, an oxo group (=O group) and a hydrogen atom are not included in the number of atoms, but carbon atoms, ether type oxygen atoms, and nitrogen atoms constituting the connecting main chain are included in the number of atoms. Therefore, -COO and -CONH- are counted as having two atoms. Similarly, for example, if Q is -CQIII4
, hydrogen atoms are not included in the number of atoms, but carbon atoms are included.

Therefore, in this case, the number of atoms is counted as 9.

More specifically, monomer (B) can be exemplified by the following compounds.

(II-1) (■ CI+.

L CI+□ C00(CIlz)zOcOcqll+qC00(C1
1□) 1゜COOC8+1(n-2) (■ C11゜Cl1zCOOCH3 CI+□ C00(CI+□)20COC1 11□3 (It-3) (■ 1lll CH3 C++Z=C CI+□ C00(C1l□hOc o(C)1 .＞50 COCIL
+C0NII (CILz) 6COOCIItl(■ (■ C1+3 CH7 C00(CII2) .0COC&+113 Coo (CII2) 2NHCO(CI+2) ,C
00C113 (■ (II-12) C11゜CI+□ CI+□ Coo (CHz) JCOCII H COOC8+1 C0NC1hC1hOCOCsH++ C11□CIl□0COC311゜(II-10) CH:1 (II-1 3) CIl□=C CH3 COOCII□ClCl1zOCOCsH++0COC
5H.

(n-11) (u-14) CH2=C C11゜C00CIL+CIICHZOCOC611OCOC3
1h CH=C11 C00(C1h)+. 0COC61(+3(■ (■ CH.

CH2=C C11゜C0NIICCHzOCOC411q CIl□0COC4H9 (II-16) (■ CI+3 (■ C11□ C) I OCO(C1lz)+oOcOcJt (II-21) Hi (■ CII2=C C00CII □CHzCHOCOCsH+ +0COC
, I+□ (n-22) (■ CH11 CH2 C00C112C11CH200CCI12CHICO
OC, H9ococ:vt (■ C1l□-C1l-CIl□-OCO(CI(z) z
cOOcII□cncuzococauq(■OCOC4119 1h CH2=C (II-27) COOCHzC1hCHCII□0COC41(900
CCH-OCOCJt CH2 C0CJt (■ (■ Cfl+ C)13 C1l□ C00CII□CII CII□NHC411qOCO
C&)+13 (n-29) C11゜The dispersion resin of the present invention consists of at least one each of monomer (A) and monomer (B), and the important thing is that it can be synthesized from these monomers. If the resin is insoluble in the non-aqueous solvent,
A desired dispersed resin can be obtained. More specifically,
The monomer (B) represented by general formula (II) is preferably used in an amount of 0.1 to 30 weight percent, more preferably 0.2 to 10 weight percent, relative to the monomer (A) to be insolubilized. %. Further, the molecular weight of the dispersion resin of the present invention is preferably 10' to
! O'=, more preferably 104 to 10h.

To produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stabilizing resin, monomer (A), and monomer (B) are mixed in a non-aqueous solvent with peroxide. benzoyl,
The polymerization may be carried out by heating in the presence of a polymerization initiator such as azobisisobutyronitrile or butyllithium.

Specifically, a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, monomer (A), and monomer (B), a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, and a method of adding a polymerization initiator to a solution of a dispersion stabilizing resin dissolved A) and the monomer (B) are added dropwise together with a polymerization initiator, or the entire amount of the dispersion stabilizing resin is added to the monomer (A) and the monomer (B).
), a method in which the remaining monomer mixture is optionally added together with a polymerization initiator into a mixed solution containing a part of the mixture of There are methods such as adding optionally along with a polymerization initiator.
It can be manufactured using any method.

The total amount of monomer (A) and monomer (B) is 10% of the nonaqueous solvent.
The proportion is 3 to 80 parts by weight, preferably 5 to 50 parts by weight.

The amount of the soluble resin as a dispersion stabilizer is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total monomers used above.

The amount of polymerization initiator is 0.1 to 5% (weight) of the total monomer amount
is appropriate.

Further, the polymerization temperature is about 50 to 180°C, preferably 60 to 120°C. The reaction time is preferably 1 to 15 hours.

When the above-mentioned polar solvents such as alcohols, ketones, ethers, and esters are used in combination with the nonaqueous solvent used in the reaction, or when the monomer (A) or monomer (B) to be polymerized and granulated is ) If unreacted substances remain, it is preferable to remove them by heating the solvent or monomer to a temperature higher than its boiling point or distilling it off, or by distilling it off under reduced pressure.

The non-aqueous latex particles produced as described above exist as fine particles with a uniform particle size distribution, and at the same time exhibit extremely stable dispersibility, especially after repeated use over a long period of time in a developing device. It has good properties and is easy to redisperse even when the development speed is increased, and no stains are observed on various parts of the device.

Furthermore, when fixed by heating or the like, a strong film was formed and exhibited excellent fixing properties.

Furthermore, the liquid developer of the present invention speeds up the development and fixation process, and has excellent dispersion stability, redispersibility, and fixation properties even when a large-sized master plate is used.

If necessary, a coloring agent may be used in the liquid developer of the present invention.

The coloring agent is not particularly limited; various conventionally known pigments or dyes can be used.

When coloring the dispersion resin itself, for example, one method of coloring is to physically disperse the dispersion resin using pigments or dyes, and there are a large number of known pigments or dyes. There is. Examples include magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hanzaiero, quinacridonelend, and phthalone aniline.

Another coloring method is disclosed in Japanese Patent Application Laid-open No. 57-4873.
There is a method of dyeing the dispersed resin with a preferred dye, as described in No. 8 and others. Alternatively, as another method, there is a method of chemically bonding a dispersion resin and a dye, as disclosed in JP-A-53-54029, or as described in JP-B No. 44-22955, etc.
When producing by polymerization granulation method, there is a method of using a monomer containing a dye in advance to form a copolymer containing the dye.

Various additives may be added to the liquid developer of the present invention, as necessary, in order to strengthen charging characteristics or improve image characteristics. Those specifically described in No. 2, page 44 are used.

For example, di-2-ethylhexyl sulfosuccinate metal salt,
Examples include naphthenic acid metal salts, higher fatty acid metal salts, lecithin, poly(vinylpyrrolidone), and copolymers containing half-maleic acid amide components.

The amounts of each main component of the liquid developer of the present invention are explained below.

The toner particles mainly composed of resin (and optionally used colorant) are preferably 0.5 parts by weight to 50 parts by weight based on 1000 parts by weight of the carrier liquid.

If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, fogging will tend to occur in non-1iTii image areas.

Furthermore, the above-mentioned carrier liquid soluble resin for dispersion stabilization may be used if desired, and the amount of the resin may be 0.5 parts per 1000 parts of the carrier liquid.
Approximately 100 parts by weight can be added. The charge control agent as described above is used in an amount of 0 per 1000 parts by weight of the carrier liquid.
．． 001311! :ffi parts to 1.0 parts by weight are preferable.

Furthermore, various additives may be added as desired, and the upper limit of the total amount of these additives is regulated by the electrical resistance of the developer. That is, if the electrical resistance of the liquid developer with toner particles removed becomes lower than 109 Ωcm, it becomes difficult to obtain a high-quality continuous tone image.
It is necessary to control within this limit.

(Example) Examples of the present invention are illustrated below, but the present invention is not limited thereto.

1: A volume of a mixture of 100 g of P-1 octadecyl meccrylate, 150 g of toluene, and 50 g of isofurobanol was heated to a temperature of 75°C under a nitrogen stream. While stirring. , 44'-
Azobis(4-cyanovaleric acid) (abbreviations: A, C.

Add 2.0g of V,) and react for 6 hours, and further add A, C, V,
0.5g of was added and reacted for 4 hours. After cooling, it was reprecipitated into 32 methanol, collected by filtration, and dried to obtain 83 g of white powder.

A mixture of 50 g of the above powder and 100 g of toluene was heated to a temperature of 40'C and dissolved under stirring. Next, L-
Butylhydroquinone 0.2g, vinyl acetate 3.0g,
0.025 g of mercury acetate was added and reacted for 2 hours.

Then raise the temperature to 70°C and add 100% sulfuric acid 3.4XIQ.
-3rd was added and reacted for 18 hours. After the reaction, 0.02 g of sodium acetate trihydrate was added to the reaction solution for 30
After stirring for a minute, the mixture was cooled and reprecipitated into 1.5 ml of methanol. 38 g of slightly brownish powder was obtained.

The weight average molecular weight of this powder was 88,000.

Resins P-2 to P-10 were produced in the same manner as in Production Example 1, except that the monomers shown in Table 1 below were used instead of the monomers shown in Table 1 below.

In production example 1, inside the octadecyl methacrylate
98.5 g of p-tiO octadecyl methacrylate, 1.5 g of thioglycolic acid
A mixed solution of 100 g of toluene and 100 g of toluene was heated to a temperature of 75° C. under a nitrogen stream. 0.4 g of 1.1'-azobis(cyclohexane-1-carbonitrile) was added and reacted for 5 hours, and further, 0.3 g of the above azobis compound was added and reacted for 5 hours. After adding 0.4 g of t-butylhydroquinone to this reaction product, 5.0 g of vinyl propionate and 0.8 g of tetrabutoxytitanium were added while keeping the same temperature.
After 15 hours of reaction, the mixture was reprecipitated into methanol 31 to obtain 78 g of slightly brownish powder. The weight average molecular weight of this powder was 68,000.

No. 12: A mixed solution of 100 g of P-12 dodecyl methacrylate 1 and 200 g of tetrahydrofuran was heated to 65° C. under a nitrogen stream. 4 g of 2.2'-azobis(4-cyanovaleric acid chloride) was added and stirred for 10 hours.

The reaction solution was cooled to a temperature of 25°C or less in a water bath, and 2.4 g of allyl alcohol was added. 2.5 g of pyridine was added dropwise without exceeding the reaction temperature of 25° C., and the mixture was stirred for 1 hour. After further stirring at a temperature of 40° C. for 2 hours, the mixture was reprecipitated into methanol 21. A pale yellow viscous substance was separated by decantation and dried. The yield was 80 g and the weight average molecular weight was 45.000.

Control 13: A mixture of 100 g of P-13's hexadecyl methacrylate, 150 g of ) toluene and 50 g of ethanol was heated at a temperature of 75°C under a nitrogen stream.
heated to. Press i, A, C, V, 3. Add Og, 6
After reacting for 4 hours, 0.5g of Sarani A, C, and V were added and reacted for 4 hours.Next, it was reprecipitated in methanol 31, methanol was separated with decanethisilane, and the remaining viscous substance was dried. .

A mixed solution of 50 g of this viscous substance, 6.0 g of allyl alcohol, 0.1 g of hydroquinone, and 100 g of toluene,
The mixture was stirred at room temperature to form a homogeneous solution. 0.3 g of concentrated sulfuric acid was added to this homogeneous solution and heated to a temperature of 110°C. The reaction was carried out while removing the distilled water using a Dean Sook apparatus. After reacting for 24 hours, the mixture was cooled and reprecipitated into methanol 31, methanol was removed by decantation, and the remaining slightly brownish viscous substance was dried. The yield was 138 g and the weight average molecular weight was 56,000.

In Production Example 12, resins P-14 to P-19 were produced in the same manner as in Production Example 12a, except that the monomers shown in Table 2 below were used instead of dodecyl meccrylate.

Inside” 20: P-
20+1゛1 octadecyl methacrylate 100g
A mixed solution of 150 g of toluene and 50 g of ethanol was heated to a temperature of 70° C. under a nitrogen stream. While stirring, 2,0g of ^, C, and V were added and reacted for 6 hours.
, V, was added and reacted for 4 hours.

After cooling, it was reprecipitated in methanol 3P, collected as a fly, and dried to obtain 85 g of white powder.

50 g of the above powder, 3.7 g of glycidyl methacrylate,
2.2'-methylenebis-(6-L-butyl-p-cresol) 1.0g, N,N-dimethyldodecylamine 0
．． A mixture of 5g and 100g of toluene was heated to 100°C.
and stirred for 12 hours. This reaction? The 1% compound was reprecipitated in 1.52 methanol, and the pale yellow powder was collected and dried. Yield: 39g, weight average molecular weight: 35,00
It was 0.

'～' 21: P-2
A mixed solution of 100 g of 19 octadenyl methacrylate No. 1 and 200 g of tetrahydrofuran was heated to a temperature of 70° C. with stirring under a nitrogen stream. 4,4'-azobis(
5 g of 4-cyanopentanol) was added and reacted for 5 hours.

Furthermore, the above azobis compound] and Og were added and reacted for 5 hours. The reaction mixture was cooled to a temperature of 20°C in a water bath and added with 3.2 g of pyridine and 2.2'methylenebis-(6-
1.0 g of t-butyl-p-cresol) was added and stirred. 4.2 g of methacrylic acid chloride was added dropwise to this mixed solution over 30 minutes while keeping the reaction temperature from exceeding 25°C. Stirred for 4 hours at a temperature of 20'C to 25C. Next, this reaction product was reprecipitated in a mixed solution of methanol 1.51/water 0.51, and the white powder was filter-dried. The yield was 86 g and the weight average molecular weight was 33,000.

In Production Example 21, each dispersion stabilizing resin P-22 to P-3 was prepared in exactly the same manner as in Production Example 21, except that the acid chloride shown in Table 3 below was used instead of methacrylic acid chloride.
1 was manufactured. The weight average molecular weight of each resin is 30,000
~40,000.

The polymerization rate of each particle was 85 to 90%.

Table-4 12g of dispersion stabilizing resin P-1, 100g of vinyl acetate,
A mixed solution of 1.5 g of Compound Example 11-19 (monomer (B)) and 4 g of Isopar H3B was heated to 70° C. with stirring under a nitrogen stream. 2.2'-Azobis(isovaleronitrile) (abbreviations: A, 1.V, N,) at 0.
8g was added and reacted for 6 hours. 20 minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88°C. temperature to 100
The temperature was raised to .degree. C. and stirred for 2 hours, and unreacted vinyl acetate was distilled off.

After cooling, the white dispersion obtained by passing through 200 mesh nylon cloth had a polymerization rate of 86% and an average particle size of 0.20I! It was latex of m.

In production example 1 of latex particles, dispersion stabilizing resin P
-1 and monomer (B) in place of compound example ■-19,
Each latex particle was produced in the same manner as in Production Example 1, except that the dispersion stabilizing resin and monomer (B) listed in Table 4 below were used.

Table 4 (continued) The solvent and residual vinyl acetate were distilled off. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.20.

8 g of resin P-25 obtained in Production Example 25 of resin for dispersion stabilization
(as solid content), poly[dodenyl methacrylate]
A mixed solution of 7g of vinyl acetate, 100g of vinyl acetate, 1.5g of monomer (B) compound example 1-15, and 380g of n-decane was heated to 75°C with stirring under a nitrogen stream.

2.2'-azobis(isobutyronitrile) (abbreviation; ^
, 1. 1.0g of B, N,) was added and reacted for 4 hours, and then A, 1. 0.5g of B and N were added and reacted for 2 hours. The temperature was raised to 110"C and stirred for 2 hours, and 14 g of resin P-1 obtained in Production Example 1 of low boiling point dispersion stabilizing resin, 85 g of vinyl acetate, and 2 of compound example ■-23 of monomer (B) were added. .0g,
15g N-vinylpyrrolidone and 400g isododecane
The mixed solution was heated to 65°C with stirring under a nitrogen stream. A.1. 1.5g of B and N were added and reacted for 4 hours. After cooling, it was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.26 μm.

12 g of resin P-5 obtained in Production Example 5 of resin for dispersion stabilization,
Vinyl acetate loog, compound example of monomer (B) ■-18
1.5 g, 5 g of 4-pentenoic acid and Isopar 03
83 g of the mixed solution was heated to a temperature of 6 while stirring under a nitrogen stream.
Warmed to 0°C. A.1. V, N, 1. Og was added and the mixture was reacted for 2 hours. Furthermore ^, 1. 0.5g of V and N were added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth and was a latex with an average particle size of 0.25-.

Resin P'-20 obtained in Production Example 20 of resin for dispersion stabilization was
08. A mixed solution of 2 g of monomer (B) compound example ■-16, 100 g of methyl methacrylate, and 478 g of Isopar H was heated to a temperature of 65"C with stirring under a nitrogen stream.A, 1.V, N , and reacted for 4 hours. After cooling, coarse particles were removed through a 200 mesh nylon cloth, and the resulting white dispersion was a latex with an average particle size of 0.36.

Resin P-21 obtained in Production Example 21 of resin for dispersion stabilization was
g, 100 g of styrene, compound example of monomer (B) ■-2
A mixed solution of 4 g of 2 and 380 g of Isopar H was heated to 50° C. with stirring under a nitrogen stream.

1. Solid content of n-butyllithium hexane solution.
An amount of 0 g was added and the reaction was continued for 4 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth and was a latex with an average particle size of 0.30.

-Tex's ``'28 A poly[occudecyl methacrylate] (weight average molecular weight 135,00
0), 100 g of vinyl acetate, 1.5 g of monomer (B) compound example ■-19, and 380 g of Isopar H.
Processing was carried out in the same manner as in latex particle production example 1 except for using a mixed solution of
A white dispersion of 1 m latex particles was obtained.

Larx's "-29B" 14g of dispersion stabilizing resin with the following structure, 100g of vinyl acetate
The process was carried out in the same manner as in Production Example 1 of latex particles except that a mixed solution of 1.5 g of monomer (B) compound (B) -19 and 6 g of Isopar H3B was used to obtain a polymerization rate of 90% and an average particle size of 0. A white dispersion of 25- latex particles was obtained.

Comparative liquid developer Example 1 and Comparative Examples A-B Dodecyl methacrylate-acrylic acid copolymer [Copolymerization ratio (95/5) weight ratio] log, nigrosine 10
g and 30 g of Shersol 71 were placed in a paint shaker (Tokyo Seiki ■) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

30g of resin dispersion D-1 of latex particle production example 1
, 2.5 g of the above nigrosine dispersion, 0.08 g of occudecene-half-maleic acid octadecylamide copolymer,
F OC-1400 (manufactured by Nissan Chemical ■, higher alcohol H
An electrostatic photographic liquid developer was prepared by diluting 5 g of Schersol 71 to 11.

(Comparative Example Developer AB) In the developer production example described above, two types of resin dispersions D-1A-B were prepared.

Comparative liquid developer A: Resin dispersion of production example 28 of latex particles Comparative liquid developer B Resin dispersion of production example 29 of latex particles ELP Master ■ type (manufactured by Fuji Photo Film ■), which is an electrophotographic light-sensitive material, was exposed and developed. The plate making speed was 5 plates/min. Furthermore, after processing 2,000 sheets of the ELP master ■ type, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image was determined using a 30% original. The results are shown in Table-5.

Table 5 When plate making was performed using each developer under the plate making conditions described above, as is clear from the results in Table 5, there was no staining of the developing device and the image on the 2,000th plate making plate was clear. The developer having the following properties was only the developer of the present invention.

On the other hand, a master plate for offset printing (iLp-master) obtained by making a plate using each developer was printed using a conventional method, and the number of prints was calculated until characters were missing or fading in solid areas occurred in the image of the printed matter. As a result of comparison, no problem occurred in the master plates obtained using the developers of the present invention and Comparative Examples A to B even when the number of master plates was 10,000 or more.

As shown in the above results, only the developer made from the resin particles of the present invention completely (does not cause) stains on the developing device.
The number of printed master plates was also good.

That is, in the case of Comparative Examples A and B, there was no problem with the number of prints, but the developing device was so dirty that it could not withstand continuous use.

These results demonstrate that the resin particles of the present invention are clearly superior.

Example 2 White dispersion D-2 obtained in latex particle production example 2
A mixture of 100 g of Sumikalon Black and 1.5 g of Sumikaron Black was heated to 100° C. and stirred for 4 hours. After cooling to room temperature, the remaining dye was removed by passing it through a 200 mesh nylon cloth to obtain a black resin dispersion with an average particle size of 0.20 Jm.

32g of the above black resin dispersion, 0 zirconylam naphthenate
．． A liquid developer was prepared by diluting 0.05 g of Shersol 71 IN.

When this was developed using the same apparatus as in Example 1, the result was 2.0
Even after developing 00 sheets, no toner adhesion stains occurred on the device.

Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.

Example 3 White dispersion D- obtained in latex particle production example 25
A mixture of 100 g of No. 25 and 83 g of Victoria Blue was heated to a temperature of 70°C to 80°C and stirred for 6 hours.

After cooling to room temperature, the remaining dye was removed by passing it through a 200 mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0.26.

32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 0.05 g in Isopar HIN.

When this was developed using the same apparatus as in Example 1, the result was 2.0
Even after developing 00 sheets, no toner adhesion stains were observed on the device. Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.

Example 4 White resin dispersion D-2 obtained in latex particle production example 2
A liquid developer was prepared by diluting 32 g of nigrosine dispersion obtained in Example 1, 2.5 g of the nigrosine dispersion obtained in Example 1, and 0.02 g of a semi-docosanylamidated product of a copolymer of octadecyl vinyl ether and maleic anhydride in 11 liters of Isopar G.

When this was developed using the same device as in Example 1, 2.
Even after developing 1,000 sheets, no toner adhesion stains were observed on the device. In addition, the image quality of the obtained master plate for offset printing and the image quality of printed matter after printing 10,000 sheets were both clear.

Furthermore, after leaving this developer for three months, the same treatment as above was performed, but there was no difference at all from before aging.

Example 5 10g of poly[decyl methacrylate], Isopar H
30 g and 8 g of alkali blue were placed in a paint shaker together with glass beads and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

30 g of white resin dispersion D-10 obtained in latex particle production example 10, and the above alkali blue dispersion 4.2.
g, and 0.06 g of a semi-docosanylamidated copolymer of diisobutylene and maleic anhydride to Isopar G1f.
A liquid developer was prepared by diluting it to f1.

When this was developed using the same apparatus as in Example 1, the result was 2.0
Even after developing 00 sheets, no toner adhesion stains were observed on the device. In addition, the image quality of the obtained master plate for offset printing and the image quality of printed matter after printing 10,000 sheets were both very clear.

Examples 6-22 In Example 5, white resin dispersion D of latex particles
A liquid developer was prepared in the same manner as in Example 5, except that the latex particles shown in Table 6 were used in place of 10 in an amount giving a solid content of 6.0 g.

Table 6 When this was developed using the same device as in Example 1, the result was 2.0
Even after developing 00 sheets, no toner adhesion stains were observed on the device. Furthermore, both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after printing 10,000 sheets were very clear.

(Effects of the Invention) According to the present invention, a developer with excellent dispersion stability, redispersibility, and fixing properties was obtained. In particular, even when used under plate-making conditions with extremely high plate-making speeds, the developing device did not become contaminated, and both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after printing 10,000 sheets were very clear. Ta.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 10^9 Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles are as follows: A monofunctional monomer (
A monofunctional monomer that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization in the presence of a dispersion stabilizing resin that has a polymerizable double bond group that can be copolymerized with A). body (A), and the following general formula (II)
At least one monomer (B) containing at least two polar groups and/or polar linking groups represented by
A liquid developer for electrostatic photography, characterized in that it is copolymer resin particles obtained by subjecting a solution containing seeds to a polymerization reaction. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula (I), X is -COO-, -OCO-, -C
H_2OCO-, -CH_2COO-, -O-, or -
Represents SO_2-. R^1 represents an aliphatic group having 6 to 32 carbon atoms. a^1 and a^2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-R^2, or a carbonized group having 1 to 8 carbon atoms. -COO-R^2 (R^2 has 1 or more carbon atoms) via a hydrogen group
22) represents a hydrocarbon group. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In general formula (II), V is -O-, -COO-, -OCO
-, -CH_2OCO-, -SO_2, -CONH-,
-SO_2NH-, ▲Mathematical formulas, chemical formulas, tables, etc.▼
, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (W is a hydrocarbon group or a bonding group in general formula (II): ▲ Numerical formulas, chemical formulas,
There are tables, etc. Represents the same content as ▼. ) Q is a hydrogen atom or a halogen atom, -OH, -CN,
-NH_2, -COOH, -SO_3H or -PO
_3 Represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with H_2. X_1 and X_2 may be the same or different from each other,
-O-, -S-, -CO-, -CO_2-, -OC, respectively
O-, -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, -NHCO
_2- or -NHCONH- (Q_1, Q_2
, Q_3, Q_4, and Q_5 indicate the same contents as Q above). U_1 and U_2 may be the same or different from each other,
Each may be substituted, or ▲There is a mathematical formula, chemical formula, table, etc.▼ may be interposed in the bond of the main chain [X_3, X_4 are
They may be the same or different from each other, and have the same contents as X_1 and X_2 above, U_4 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and Q_6 has the same contents as Q above.] Represents a hydrocarbon group having 1 to 18 carbon atoms. b_1 and b_2 may be the same or different, and each represents a hydrogen atom, a hydrocarbon group, -COO-L, or -COO-L via a hydrocarbon (L is a hydrogen atom or an optionally substituted hydrocarbon group) ). m, n and p may be the same or different and each represents an integer from 0 to 4.